JPS61204354A - Alloy for sealing glass - Google Patents

Abstract

PURPOSE:To obtain the titled alloy having low thermal expansion, coefft. superior glass sealability and capable of sealing against glass efficiently, by composing it with respective prescribed ratios of Ni, Cr, C, O, N, P, S and the balance Fe with inevitable impurities. CONSTITUTION:The titled alloy is composed of, by weight% 30-<37% Ni, 1-10% Cr, <=0.1% C, <=0.1% C, <=0.1% O, <=0.025% N, <=0.05% P,<=0.05% S, and the balance Fe with inevitable impurities. The alloy has equal thermal expansion characteristic to that of conventional 42% Ni - 6% Cr - Fe alloy having superior low said characteristic, further, formation of Fe3O4 having strong bonding force with glass is facilitated by decreasing nonferrous element. Consequently, procedure effect of glass sealing is improved, and alloy having sunthetic sealability superior than that of 42% Ni - 6% Cr - Fe alloy is obtd. Since the alloy has lower content of precious Ni than conventional, it is inexpen sive in cost and is extremely superior alloy.

Description

[Detailed description of the invention] purpose of invention The present invention relates to an alloy for sealing soft glass.

Conventional technology and problems Conventionally, as an alloy used for sealing with soft glass,
421Ni-61Cr-AE alloy is often used because it has a coefficient of thermal expansion that matches that of soft glass and has good sealing strength. This conventional 42% Ni-6 bag C! When sealing the r-Fe alloy, Cr is preferentially oxidized in wet hydrogen as a preliminary treatment, and then the alloy is sealed with glass in the atmosphere.

At this time, Pe304, which has a strong bonding force with glass, is formed, and good sealing strength with glass is obtained. However, 42
1GNi-4%0r-a alloy has non-ferrous elements of N1 and Cr.
Since it also contains 48- in total, 1In normal processing, lFe3
Also, the formation of O4 is not sufficient.

There was a drawback that it took too much time to sufficiently form Ire, 04.

The present invention has been made in view of this point, and it is an object of the present invention to provide an alloy that has a low coefficient of thermal expansion, excellent glass sealing properties, and can be efficiently sealed with glass. i.e. 9 wt-, N130-37%, Crl ~10%, O[L
l- or less, O (100.015% or less, Nα025
- Below, P[LO5% or below, Sα05- or below, remaining IP
Glass sealing alloy consisting of e and unavoidable impurities, and N150 to less than 37 in weight, Crl to 101
G, Oα1 attack or less, O[LO151G or less, Nα0
25- or less, Pα05- or less, s [Lns arrogance or less, 8101-1% as a subcomponent, Mn (%-1%, AXα05
One or more of ~1-.

An alloy for glass sealing consisting of the balance A and unavoidable impurities, and a weight ratio of N130 to less than 37-, Cr1 to 10
(1, Oα1S or less, 0 (LO15 or less.

MO, Q25- and below, I'a05- and below, 8 (LQ51
! Below, Ti (over LO5~%.ZrCL0
5-1s, It) 105-%1. OuαQ1~21&,
M.

α01~5%, Mg1Q 1~CL5%, Gaα
01~(LSI, 7CL01~(L51!, B(LO(
A glass sealing alloy consisting of one or more of 1°5 to a2-, the remainder 1e and unavoidable impurities, and Ni30 to less than 37% by weight, 0r1-10%. O0
．． 1 or less, 0 (L00.015% or less, Nα025%
Below, pluss or less, 5cLas* or less, S1α1~%% as a subcomponent. Mn%~1-. M%05~
One or more of %1 and more than %05-1'f
4. Zr(105-1 饅, WbαQ5-1 regret.

0u001~21. Moα01~5%, Mgα01~α
5 悌, ○aα01~α5chi, Vα01~α5chi.

One or more types of BαOOS to α21g.

The present invention relates to an alloy for glass sealing consisting of the remainder 1Fc5 and unavoidable impurities, and an alloy for glass sealing whose crystal grain size is equal to or larger than grain size number &0.

Effects of the invention As a result, 42SNi, which has conventional excellent low thermal expansion properties,
Thermal expansion properties are equivalent to those of -6T Cr-Fe alloy.

Moreover, the reduction in non-ferrous elements results in a stronger bond with glass. elO, is easily formed, increasing the work efficiency of glass sealing and improving overall sealing performance.
An alloy superior to the r-er alloy was obtained.

Furthermore, since the alloy of the present invention contains less expensive N1 than the conventional alloy, it is also cheaper in terms of cost.

It is an extremely excellent alloy.

Next, the reasons for limiting the composition of the alloy of the present invention will be explained.

N1 has the greatest influence as an element that adjusts compatibility with glass, that is, adapts it to the thermal expansion characteristics of glass. If Ml is less than 3 on, the thermal expansion coefficient will be high and the thermal expansion characteristics will not be compatible with glass.

Also, is the content of non-ferrous elements too high for 37 or more? e,04 becomes difficult to form and is also economically disadvantageous. For this reason, the M1 content was set to less than 30 to 37 seconds.

Cr is an element that greatly affects compatibility with glass and sealing strength. As the content of Cr increases, the coefficient of thermal expansion increases. Therefore, by controlling the contents of N1 and Cr in accordance with the glass used for sealing, it is possible to finely adjust the thermal expansion characteristics of the alloy of the present invention to the optimum one. However, if the Cr content exceeds 1091, the coefficient of thermal expansion becomes too large, making it unsuitable for glass sealing. In addition, prior to sealing the alloy of the present invention with glass, an oxide film is formed on the surface as a preliminary treatment, and the glass is sealed via this oxide film, but the sealing strength is determined by the bonding strength between this oxide film and the alloy base metal. It also depends on the adhesion. In order to improve the adhesion between the oxide film and the alloy base metal, it is necessary to preferentially oxidize chromium and form a chromium oxide film in the preliminary treatment. For this purpose, the Cr content must be 1 or more.

Based on the above, the Cr content was determined to be 1 to 10.

○ (%) If the content exceeds %, air bubbles are likely to form in the glass during sealing, significantly deteriorating the sealing strength.For this reason,
The upper limit of O content was defined as (Ll-.

0 is an element that greatly affects the formation of an oxide film and sealing, and if it is contained in an amount exceeding 100.015%.

The oxide film becomes uneven and the density of the oxide film deteriorates, resulting in a significant loss of sealing strength. Also.

In the worst case, bubbles may be formed in the glass during sealing, which is undesirable. Therefore, the upper limit of the 0 content was set at 0,015 yen.

Like 0, N is an element that greatly affects sealing properties, and CLO
If the N content exceeds 25%, the sealing strength will be significantly impaired, so the upper limit of the N content was set at QJ)25.

If P is contained in an amount exceeding α05-, oxidation unevenness tends to occur, so the upper limit was set at %05-.

If S exceeds α05-, oxidation unevenness tends to occur, and the adhesion between the oxide film and the base metal decreases, so the upper limit should be set to 1.
05-.

Next, as a subcomponent, 81 forms a concentrated layer of 81 between the Cr oxide layer and the base metal during oxidation treatment.

Although it improves the adhesion between the oxide film and the base metal, it is not effective if L% is less than 1. If the content exceeds 1$, the thermal expansion characteristics change and workability deteriorates, which is not preferable.

Mn forms an oxide with good glass wettability on the outer layer of the oxide film, improving the wettability between the oxide film and glass, but α1s
If the amount is less than 1, it is ineffective, and if it is contained in excess of 1 cup, the oxidation rate becomes high and the oxide desert becomes too thick, making it unsuitable for sealing.

A1 improves the adhesion strength between the oxide film and the alloy base metal, but α
If the content is less than 0.05%, there is no effect; if the content exceeds 1%, the thermal expansion characteristics change, which is not preferable.

It is also effective to add a trace amount of an element that further improves the sealing properties. That is, Ti(105
Super~1 Bun, Zr[LO5~1-, Wb[105~
%. Cuα01-2%, NoαQ1-5-, Mgα01
~15%, 0a(Lol ~α5-2v(LOl ~(
15%, B (one or two of LOO5 to IIL2-
When more than one species is contained, the sealing properties are further improved.

The reason for adding these subcomponents and the reason for limiting the range of the components will be described below.

T1 improves the adhesion between the oxide film and the base metal.

(If the LO is less than 5-, there is no effect, and if it exceeds 1, the processability becomes poor and the oxide film tends to become uneven.

Zr improves the adhesion between the oxide film and the base metal and the wettability of the oxide film with glass, but it has no effect when it is less than 105-
If it exceeds s, workability will be impaired.

Nt) improves the adhesion between the oxide film and the base metal.

If it is less than α05-, there is no effect, and if it exceeds 1 cup, processability will be impaired.

Cu makes the oxide film dense and improves sealing properties.

If it is less than α01, there is no effect, and if it exceeds α01, the oxide film becomes too thick and becomes unsuitable for sealing.

Mo improves the adhesion between the oxide film and the base metal.

(If it is less than 10%, there is no effect, and if it exceeds 3%, workability is impaired and oxidation unevenness is likely to occur.

Mg improves the adhesion between the oxide film and the base metal and the wettability of the oxide film with glass, but it has no effect when α is less than α01−.
If it exceeds 5-, the oxide film becomes too thick, which is not preferable.

Although Oa improves the adhesion between the oxide film and the base metal.

[If it is less than L0%s, there is no effect, and if it exceeds α5-, oxidation unevenness tends to occur, which is not preferable.

V improves the adhesion between the oxide film and the base metal.

If it is less than α01-, there is no effect, and if it exceeds α5, workability is impaired and oxidation unevenness is likely to occur.

B improves the adhesion between the oxide film and the base metal and the wettability between the oxide film and the glass, but it has no effect at less than aoos-, and α2
If it exceeds -, oxidation unevenness tends to occur.

The two alloy components of the present invention have been explained above.

By properly controlling the grain size of these alloys,
It was confirmed that even better sealing properties could be stably obtained. That is, when the crystal grain size is equal to or larger than the grain size number aO, excellent sealing properties are obtained.

Next, the present invention will be explained in detail using examples.

Examples Tables 1 and 2 show examples of the alloys of the present invention and comparative examples. After each alloy was vacuum melted and cast, heat treatment and rolling were repeated to produce a plate material with a thickness of 13M. The thermal expansion coefficient of this sample was also measured.

The sealing strength was determined by degreasing the surface of this sample, heating it in wet hydrogen at 1050℃ for 20 minutes to form an oxide film on the surface, then sealing it with glass, and determining the adhesion strength by a tensile test. It was evaluated.

Samples 1 to 28 are alloys of the present invention, and comparative alloys A29 to 36 are alloys of the present invention. The alloy of the present invention has a coefficient of thermal expansion α
50-350 is well compatible with Shigarasu at 7 to 12 X I Q -@/℃, and the adhesion strength is 4. OK4/
-It is highly suitable as a sealing alloy. Among them,
81. Mn, Al-containing Muro-12 and 413-17 with added elements such as T1 have an adhesion strength of 5.0 noodles/- or more p 8 i r Mn * %8-28 with added elements such as A1 and T1 exhibits an adhesion strength of &5-/- or more, making it ideal for sealing alloys. In contrast, comparative alloy 12
9 to 55 are out of the component range of the present invention, so the coefficient of thermal expansion is too high or too low, or the adhesion strength is insufficient and is not suitable as a sealing alloy. Mu36 is 42S
Although it is a Ni-6%0r-Pe alloy, its overall adhesion strength is inferior to that of the alloy of the present invention.

Next, regarding the influence of crystal grain size, Table 3 shows the results of a test using 44.9.27 as a test material.

It can be seen from Table 3 that as the crystal grains become smaller, the adhesion strength improves. Therefore, in order to stably obtain excellent sealing properties, it is effective to set the crystal grain size to the grain size number aO or more.

As described above, the alloy of the present invention has excellent sealing properties, and the conventional 42 饅Ni-6SCr=A! It is an inexpensive and industrially extremely useful alloy that can fully replace Alloy No. 1.

Margin below

Claims (5)

[Claims] (1) Ni 30 to less than 37%, Cr 1 to 10% by weight
, C0.1% or less, O0.015% or less, N0.025
% or less, P 0.05% or less, S 0.05% or less, remainder F
An alloy for glass sealing consisting of e and unavoidable impurities. (2) Ni 30 to less than 37%, Cr 1 to 10% by weight
, C0.1% or less, O0.015% or less, N0.025
% or less, P 0.05% or less, S 0.05% or less, Si 0.1-1%, Mn 0.1-1%, Al 0.
An alloy for glass sealing consisting of one or more of 0.05 to 1%, the balance being ae and unavoidable impurities. (3) Ni 30 to less than 37%, Cr 1 to 10% by weight
, C0.1% or less, O0.015% or less, N0.025
% or less, P 0.05% or less, S 0.05% or less, Ti over 0.05 to 1% as subcomponents, Zr 0.05 to 1%, N
b0.05-1%, Cu0.01-2%, Mo0.01
~3%, Mg0.01~0.5%, Ca0.01~0.
5%, V0.01~0.5%, B0.005~0.2%
An alloy for glass sealing consisting of one or more of these, the balance being Fe and unavoidable impurities. (4) Ni 30 to less than 37%, Cr 1 to 10% by weight
, C0.1% or less, O0.015% or less, N0.025
% or less, P 0.05% or less, S 0.05% or less, Si 0.1-1%, Mn 0.1-1%, Al 0.
One or more of Ti0.05 to 1% and Ti0.05
Super ~1%, Zr0.05~1%, Nb0.05~1%,
Cu0.01-2%, Mo0.01-3%, Mg0.0
1-0.5%, Ca0.01-0.5%, V0.05-
0.5%, one or two of B0.005-0.2%
An alloy for glass sealing consisting of at least one species, the balance Fe and unavoidable impurities. (5) The glass sealing alloy according to claims (1) to (4), wherein the crystal grain size is 8.0 or more.